This invention relates to the preparation of novel polymer-supported phosphine and phosphine oxide compounds and the corresponding free compounds after cleavage from support. These compounds are useful as ligands in the preparation of metal-containing catalysts.
As is generally known in prior art, chelating phosphine compounds when bound to metal atoms are useful as catalysts. To facilitate separation of the catalysts from a chemical process, phosphorus ligands have been attached to solid supports such as polymers (xe2x80x9cSupported Metal Complexesxe2x80x9d, D. Reidel Publishing, 1985; Acta. Polymer. 1996, 47, 1; xe2x80x9cChem. Met.-Carbon Bondxe2x80x9d, Hartley, F. R (Ed), 1987, vol. 4, pp. 1163-1225; Neckers, J. Macromol. Sci., Chem. 1987, A24, 431-48). Interest in using the combinatorial xe2x80x9csplit and mix synthesisxe2x80x9d approach to generate polymer-bound ligands which could be tested as catalysts has brought to fore the importance of new chemistry with which to attach phosphine ligands to polymer supports (Balkenhohl et al., Angew. Chem., Int. Ed. Engl. 1996, 35, 2288-2337; Gilbertson et al., J. Organometallics 1996, 15, 4678-4680; Gilbertson et al., J. Am. Chem. Soc. 1994, 116, 4481-4482).
Novel processes have been discovered to prepare new compositions of matter that contain chelating phosphine compounds, including compounds of asymmetric diphosphines. Phosphine compounds have been shown to be useful when combined with transition metals as catalysts for chemical processes. The processes can also be utilized in a combinatorial scheme to produce libraries of phosphine compounds.
Addition of aldehyde in salicylaldehydes to acetylenes is known, but is unknown for addition to alkenes. (Kokai Tokkyo Koho JP 7853632; JP 76128205 Kokubo et al., J. Org. Chem. 1997, 62, 4564-4565.) The new phosphorus compounds have been shown to be useful as ligands in catalysts for the decarbonylation of the salicylaldehyde and insertion of the alkene, followed by ring closure forming a coumarin.
This invention is directed to compositions and processes to prepare polymer supported phosphine and phosphine oxide compounds and the corresponding free compounds after their cleavage from the polymer support.
More specifically, the invention is directed to a process to prepare a supported phosphine compound selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7
wherein:
SS is a solid support; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring, the process comprising the steps of:
a) contacting (i) a phosphine selected from the group consisting of XPR1R2, XR3Pxe2x80x94Axe2x80x94PR1R2, HP(xe2x95x90O)R1R2, HP(xe2x95x90O)R3xe2x80x94Axe2x80x94PR1R2, and HP(xe2x95x90O)R3xe2x80x94Axe2x80x94P(xe2x95x90O)R1R2 wherein X is a halogen, with (ii) the solid support, resulting in at least one P in the phosphine attached indirectly or directly to the solid support via one or more covalent bonds, and
b) optionally replacing one or more substituent of the group R1, R2, or R3 with any other substituent of the group R1, R2, or R3.
In all process and compositions embodiments of the invention, the preferred SS is selected from the group consisting of polyolefins, polyacrylates, polymethacrylates, and copolymers thereof.
The process is useful in producing the preferred supported phosphine compounds selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A. 
wherein:
Z is a divalent attaching group covalently attached to at least one P in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and
L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.
More particularly, this process to prepare supported phosphine compounds uses the supported phosphine compound of Formula 1A, where the process comprises the steps of:
a) contacting (i) at least 2 molar equivalents of a phosphine of the Formula XR3Pxe2x80x94Axe2x80x94PR1R2 wherein X is a halogen, with (ii) no more than one molar equivalent of Z, resulting in one P in the phosphine being covalently bonded to the Z, and
b) optionally replacing one or more substitutent of the group R1, R2, and R3 with any one or more of R1, R2, and R3. In this process the SS is more preferably polystyrene; L is xe2x80x94CH2xe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Alternatively, the process may use a supported phosphine compound of Formula 2A, with the process comprising the steps of:
a) contacting (i) a phosphine of the Formula PR1R2X wherein X is a halogen, with (ii) the solid support, resulting in one P in the phosphine being covalently bonded to Z, and
b) optionally replacing one or both of R1 and R2 with any other R1 or R2. In this process the SS is more preferably polystyrene; is xe2x80x94CH2xe2x80x94; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R1 and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aromatic or alkyl ring.
Alternatively, this process may use the supported phosphine compound of Formula 3A, with the process comprising the steps of:
a) contacting (i) no more than one molar equivalent of a phosphine of the Formula XR3Pxe2x80x94Axe2x80x94PR1R2 wherein X is a halogen, with (ii) at least two molar equivalents of Z, resulting in both of the P in the phosphine being covalently bonded to the Z; and
b) optionally replacing one or more of R1 and R2 with any one or more of R1 and R2. In this process the SS is more preferably polystyrene; L is xe2x80x94CH2xe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R1 and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Alternatively, this process may use the supported phosphine compound of Formula 4A, with the process comprising the steps of:
a) contacting (i) a phosphine of the Formula HP(xe2x95x90O)R3xe2x80x94Axe2x80x94PR1R2 with (ii) the solid support, resulting in one P in the phosphine being covalently bonded to Z; and
b) optionally replacing one or more of R1, R2, and R3 with any one or more of R1, R2, and R3. In this process the SS is more preferably polystyrene; L is xe2x80x94CH2xe2x80x94; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, Q2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Alternatively, this process may use the supported phosphine compound of Formula 5A with the process comprising the steps of:
a) contacting (i) a phosphine of the Formula HP(xe2x95x90O)R1R2 with (ii) a solid support of the formula 
xe2x80x83wherein the P in the solid support is covalently bonded to Z and Zxe2x80x2 is selected from the group consisting of alkenyls, resulting in the P in the phosphine being covalently bonded to the P in the solid support via Zxe2x80x2; and
b) optionally replacing one or more of R1, R2, and R3 with any one or more of R1, R2, and R3. In this process the SS more preferably is polystyrene; L is xe2x80x94CH2xe2x80x94; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
This invention is also directed to a process to prepare a combinatorial library of supported phosphine compounds selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7
wherein:
SS is a solid support;
A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups;
R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and
R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring, the process comprising the steps of:
a) contacting (i) one or more phosphines selected from the group consisting of XPR1R2, XR3Pxe2x80x94Axe2x80x94PR1R2, HP(xe2x95x90O)R1R2, HP(xe2x95x90O)R3xe2x80x94Axe2x80x94PR1R2, and HP(xe2x95x90O)R3xe2x80x94Axe2x80x94P(xe2x95x90O)R1R2 wherein X is a halogen, with (ii) one or more solid supports, resulting in at least one P in each phosphine attached indirectly or directly to the solid support via one or more covalent bonds, and
b) optionally replacing one or more R1, R2, or R3 with any other R1, R2, or R3.
The process is useful in producing a combinatorial library in which the preferred supported phosphine compounds are selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A 
wherein:
Z is a divalent attaching group covalently attached to at least one P in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.
More preferably, this process to prepare a combinatorial library of supported phosphine compounds uses Formula 1A with the process comprising the steps of:
a) contacting at least 2 molar equivalents of one or more phosphines of the Formula XR3Pxe2x80x94Axe2x80x94PR1R2 wherein X is a halogen, with no more than one molar equivalent of one or more of Z, resulting in one P in each phosphine being covalently bonded to the Z; and
b) optionally replacing one or more of R1, R2, and R3 with any one or more of R1, R2, and R3. In this process the SS more preferably is polystyrene; L is xe2x80x94CH2xe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Alternatively, the process may use the supported phosphine compounds of Formula 2A with the process comprising the steps of:
a) contacting one or more phosphines of the Formula PR1R2X wherein X is a halogen, with one or more solid supports, resulting in one P in each phosphine being covalently bonded to Z; and
b) optionally replacing one or both of R1 and R2 with any other R1 or R2. In this process the SS more preferably is polystyrene; L is xe2x80x94CH2xe2x80x94; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R1 and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aromatic, or alkyl ring.
Alternatively, the process may use the supported phosphine compounds of Formula 3A with the process comprising the steps of:
a) contacting no more than one molar equivalent of one or more phosphines of the Formula XR3Pxe2x80x94Axe2x80x94PR1R2 wherein X is a halogen, with at least two molar equivalents of one or more of Z, resulting in both of the P in each phosphine being covalently bonded to the Z; and
b) optionally replacing one or more of R1 and R2 with any one or more of R1 and R2. In this process SS is more preferably polystyrene; L is xe2x80x94CH2xe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R1 and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl or alkyl ring.
Alternatively, the process may use the supported phosphine compounds of Formula 4A with the process comprising the steps of:
a) contacting one or more phosphines of the Formula HP(xe2x95x90O)R3xe2x80x94Axe2x80x94PR1R2 with one or more solid supports, resulting in one P in each phosphine being covalently bonded to Z; and
b) optionally replacing one or more of R1, R2, and R3 with any one or more of R1, R2, and R3. In this process the SS is more preferably polystyrene; L is xe2x80x94CH2xe2x80x94; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Alternatively, the process may use the supported phosphine compounds of Formula 5A with the process comprising the steps of:
a) contacting one or more phosphines of the Formula HP(xe2x95x90O)R1R2 with one or more solid supports of the formula 
xe2x80x83wherein the P in the solid support is covalently bonded to Z and Zxe2x80x2 is selected from the group consisting of alkenyls, resulting in the phosphorus in each phosphine being covalently bonded to the phosphorus in the solid support via Zxe2x80x2, and
b) optionally replacing one or more of R1, R2, and R3 with any one or more of R1, R2, and R3. In this process the SS is more preferably polystyrene; L is xe2x80x94CH2xe2x80x94; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Additionally, the invention is directed at a process to prepare a phosphine compounds of Formulae 8, 9, 10, 11, and 12
wherein:
A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups;
R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle;
any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring;
the process comprising the steps of:
a) contacting (i) a supported phosphine selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7
xe2x80x83wherein:
SS is a solid support wherein at least one P in the phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometal groups; R1, R2 and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring with
(ii) a compound of the Formula ER9, wherein E is an electrophilic group and R9 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; thereby forming the corresponding compound of Formulae 1, 2, 3, 4, 5, 6, and 7; and
b) optionally replacing one or more substituent of the group R5, R6, R7, and R8 with any other substituent of the group R5, R6, R7, and R8.
More preferably, the process for preparing a phosphine compound uses a supported phosphine selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A 
wherein:
Z is a divalent attaching group covalently attached to at least one P in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms; A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring. Still more preferably in this process E is selected from the group consisting of hydrogen, PCl2, and SiMe3, and R5 is a halogen.
Also in this process, the supported phosphine compound is selected from the group consisting of Formulae 1 and 3, and the phosphine compound is of Formula 8. Also in this process at least one substitutent of the group R5, R6, R7, and R8 differs from the other substitutent of the group R5, R6, R7, and R8.
Also in this process, Z is preferably selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is preferably selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5, R6, R7,and R8 are preferably independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are preferably independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, R7, and R8 can optionally together with any other substituent of the group R5, R6, R7, and R8 form a ring.
Alternatively, the process may use the supported phosphine compound of Formula 2 and the phosphine compound of Formula 9. In this process more preferably Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5, R6, and R7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, and R7 can optionally together with any other substituent of the group R5, R6, and R7 form a ring.
Alternatively, the process may use the supported phosphine compound of Formula 4 and the phosphine compound of Formula 10. In this process more preferably Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5, R6, and R7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, and R7 can optionally together with any other substituent of the group R5, R6, and R7 form a ring.
Alternatively, the process may use the supported phosphine compound selected from the group consisting of Formulae 3 and 5, and the phosphine compound of Formula 11. In this process more preferably Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R6, R7, and R8 are independently selected from the group consisting of Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R6, R7, and R8 can optionally together with any other substituent of the group R6, R7, and R8 form a ring.
Alternatively, the process may use the supported phosphine compound of Formula 2 and the phosphine compound of Formula 12. I this process more preferably Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5 and R6 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5 and R6 can optionally together with any other substituent of the group R5 and R6 form a ring.
This invention is still further directed to a process to prepare a combinatorial library of phosphine compounds selected from the group consisting of Formulae 8, 9, 10, 1 1, and 12
wherein:
A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring;
the process comprising the steps of:
a) contacting (i) one or more supported phosphines selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7
xe2x80x83wherein:
SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring with
(ii) one or more compounds of the Formula ER9, wherein E is an electrophilic group and R9 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; thereby forming the corresponding compounds of Formulae 1, 2, 3, 4, 5, 6, and 7; and
b) optionally replacing one or more substitutents of the group R5, R6, R7, and R8 with any other substitutent of the group R5, R6, R7, and R8.
More particularly the process may use the supported phosphine compounds of the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A 
wherein:
Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms; A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.
In this process preferably E is selected from the group consisting of hydrogen, PCl2, and SiMe3, and R5 is a halogen. Additionally in this process preferably the supported phosphine compounds are selected from the group consisting of Formulae 1 and 3, and the phosphine compound is Formula 8. More preferably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.
Alternatively in this process the preferred supported phosphine compounds are of Formula 2, and the phosphine compounds are of Formula 9. More preferably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5, R6, and R7, are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2 Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, and R7 can optionally together with any other of R5, R6, and R7 form a ring.
Alternatively in this process the preferred supported phosphine compounds are of Formula 4 and the phosphine compounds are of Formula 10. More preferably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5, R6, and R7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, and R7 can optionally together with any other of R5, R6, and R7 form a ring.
Alternatively in this process the preferred supported phosphine compounds are selected from the group consisting of Formulae 3 and 5, and the phosphine compounds are of Formula 11. More preferably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R6, R7, and R8 are independently selected from the group consisting of Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, Q2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R6, R7, and R8 can optionally together with any other of R6, R7, and R8 form a ring.
Alternatively in this process the preferred supported phosphine compounds are of Formula 2, and the phosphine compounds are of Formula 12. More preferably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5 and R6 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, O2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5 and R6 can optionally together with any other of R5 and R6 form a ring.
This invention is still further directed to a supported phosphine compound selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7
wherein:
SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring.
More preferably the supported phosphine compound is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A 
wherein:
Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.
Alternatively, the preferred supported phosphine compound is Formula 1A. More preferably in this supported phosphine compound the SS is polystyrene; L is xe2x80x94CH2xe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Alternatively, the preferred supported phosphine compound is Formula 2A. More preferably in this supported phosphine compound the SS is polystyrene; L is xe2x80x94CH2xe2x80x94; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R1 and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aromatic, or alkyl ring.
Alternatively, the preferred supported phosphine compound is Formula 3A. More preferably in this supported phosphine compound the SS is polystyrene; L is xe2x80x94CH2xe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R1 and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Alternatively, the preferred supported phosphine compound is Formula 4A. More preferably in the supported phosphine compound of claim 63 the SS is polystyrene; L is xe2x80x94CHxe2x80x94; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Alternatively, the preferred supported phosphine compound is Formula 5A. More preferably in this supported phosphine compound the SS is polystyrene; L is xe2x80x94CH2xe2x80x94; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
This invention is still further directed to a combinatorial library of supported phosphine compounds selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7
wherein:
SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring.
Preferably the combinatorial library of this invention uses the supported phosphine compounds selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A 
wherein:
Z is a divalent attaching group covalently attached to at least one phosphorus in each phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.
Preferably, the combinatorial library uses the supported phosphine compounds of Formula 1A. More preferably in this combinatorial the SS is polystyrene; L is xe2x80x94CH2xe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Alternatively, the combinatorial library uses the supported phosphine compounds of Formula 2A. More preferably in this combinatorial the SS is polystyrene; L is xe2x80x94CH2xe2x80x94; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R1 and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aromatic, or alkyl ring.
Alternatively, the combinatorial library uses the supported phosphine compounds of Formula 3A. More preferably in this combinatorial library the SS is polystyrene; L is xe2x80x94CHxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R1 and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Alternatively, the combinatorial library uses the supported phosphine compounds of Formula 4A. More preferably in this combinatorial library the SS is polystyrene; L is xe2x80x94CH2xe2x80x94; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Alternatively, the combinatorial library uses the supported phosphine compounds of Formula 5A, more preferably in this combinatorial library the SS is polystyrene; L is xe2x80x94CHxe2x80x94; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
The invention is still further directed to a combinatorial library of phosphine compounds selected from the group consisting of Formulae 8, 9, 10, 11, and 12
wherein:
A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R5, R6, R7, and R8 are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; R5, R6, R7, and R8 are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ , OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, R7, and R8 can optionally together with any other substituent of the group R5, R6, R7, and R8 form a ring.
Preferably in this combinatorial library of phosphine compounds A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.
Preferably in this combinatorial library the phosphine compounds are of Formula 8. More preferably in this combinatorial library at least one of the substitutents of the group R5, R6, R7, and R8 differs from the other substituents of the group R5, R6, R7, and R8.
Alternatively in this combinatorial library of phosphine compounds A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, R7, and R8 can optionally together with any other substituent of the group R5, R6, R7, and R8 form a ring.
Preferably in this combinatorial library the phosphine compounds are of Formula 9. More preferably in this combinatorial library A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, and R7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, and R7 can optionally together with any other substituent of the group R5, R6, and R7 form a ring.
Preferably in this combinatorial library the phosphine compounds are of Formula 10. More preferably in this combinatorial library A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, and R7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, and R7 can optionally together with any other substituent of the group R5, R6, and R7 form a ring.
Preferably in this combinatorial library the phosphine compounds are of Formula 11. More preferably in this combinatorial library A is an optionally-substituted carbon chain of 1-3 carbon atoms; R6, R7, and R8 are independently selected from the group consisting of Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R6, R7, and R8 can optionally together with any other substituent of the group R6, R7, and R8 form a ring.
Preferably in this combinatorial library the phosphine compounds are of Formula 12. More preferably in this combinatorial library A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5 and R6 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5 and R6 can optionally together with any other of R5 and R6 form a ring.
This invention is still further directed to a coordination compound comprising one or more transition metals complexed to a ligand selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7
wherein:
SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometal groups; R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring.
Preferably the transition metal is selected from Periodic Group VIII.
Preferably the coordination compound is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A 
wherein:
Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene. xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.
More preferably the coordination compound is Formula 1A. In this coordination compound still more preferably the SS is polystyrene; L is xe2x80x94CH2xe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl or alkyl ring; and the transition metal is Rh.
Most preferably the coordination compound is polymer-bound 1-(1,1-di-n-propylphosphino)-2-n-propylphosphinoethane and (1,5-cyclooctadiene)-rhodium(I) chloride dimer.
This invention is still further directed to a combinatorial library of coordination compounds comprising one or more transition metals complexed to one or more ligands selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7
wherein:
SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring.
Preferably the transition metal is selected from Periodic Group VIII.
More preferably the combinatorial library is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A 
wherein:
Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.
More preferably the combinatorial library of coordination compounds is Formula 1A. In this combinatorial library of coordination compounds the SS is polystyrene; L is xe2x80x94CHxe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring; and the transition metal is Rh.
This invention is still further directed to a combinatorial library of coordination compounds comprising one or more transition metals complexed to one or more ligands selected from the group consisting of Formulae 8, 9, 10, 11, and 12
wherein:
A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of the substituents of the group R5, R6, R7, and R8 can optionally together with any other of the substituents of the group R5, R6, R7, and R8 form a ring.
More preferably in the combinatorial library A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring; and the transition metals are selected from Periodic Group VIII.
Still more preferably in the combinatorial library the ligands are of Formula 8. Still more preferably in the combinatorial library at least one substituent of the group R5, R6, R7, and R8 differs from the other substituents of the group R5, R6, R7, and R8.
Alternatively, in this combinatorial library of coordination compounds A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, R7, and R8 can optionally together with any other substituent of the group R5, R6, R7, and R8 form a ring; and the transition metal is Pd.
This invention is still further directed to a process to prepare coumarin comprising contacting salicylaldehyde with an acrylate of the formula 
wherein R10 is an alkyl group of 1-6 carbons. Preferably, the process to prepare coumarin is performed in the presence of a catalytic amount of a coordination compound comprising one or more transition metals complexed to a ligand selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7
wherein:
SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R1, R2 and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring.
Preferably, the process for preparing coumarin uses a transition metal selected from Periodic Group VIII.
Preferably in the process to prepare coumarin, the ligand is Formula 1A: 
wherein:
Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.
More preferably in the process to prepare coumarin, L is xe2x80x94CH2xe2x80x94; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring; and the transition metal is Rh.
The present invention provides for a process to prepare novel, covalently attached phosphine ligands on polymer supports. These phosphine ligands are useful as catalysts when combined with a transition metal precursor. The present invention also allows synthesis of new free phosphine ligands by chemical cleavage from the solid support.
The invention provides for novel supported phosphine compositions of Formulae 1-7: 
wherein SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds;
A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and
R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring.
By hydrocarbyl is meant a straight chain, branched or cyclic arrangement of carbon atoms connected by single, double, or triple carbon to carbon bonds and/or by ether linkages, and substituted accordingly with hydrogen atoms. Such hydrocarbyl groups may be aliphatic and/or aromatic. Examples of hydrocarbyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, benzyl, phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, vinyl, allyl, butenyl, cyclohexenyl, cyclooctenyl, cyclooctadienyl, and butynyl. Examples of substituted hydrocarbyl groups include methoxy, phenoxy, toluyl, chlorobenzyl, fluoroethyl, p-CH3xe2x80x94Sxe2x80x94C6H5, 2-methoxy-propyl, and (CH3)3SiCH2.
Virtually any solid material may be used as a support in the context of this invention as long as it meets the following criteria:
The material is insoluble in organic, aqueous, or inorganic solvents. Organic polymer supports are acceptable in this regard but they generally need to be crosslinked. Inorganic support, such as metal oxides (SiO2, Al2O3, TiO2, ZrO2, etc.), clays, and zeolites, and modified carbons are generally insoluble in these solvents and also may be used as supports.
The support contains reactive sites, which can be used for the covalent attachment of the phosphorus.
The reactive sites are isolated to prevent additional crosslinking during further chemical transformations.
The reactive sites are exposed to the reaction medium. With a polymer resin support this is achieved through the use of a resin which swells in a reaction solvent or is sufficiently porous to allow transport of the reaction medium through the polymer matrix.
The term xe2x80x9csolid supportxe2x80x9d refers to a material having a rigid or semi-rigid surface that contains or can be derivatized to contain functionality, which covalently links a compound to the surface thereof. Other modifications may be made in order to achieve desired physical properties. Such materials are well known in the art and include, by way of example, polystyrene supports, polyacrylamide supports, polyethyleneglycol supports, metal oxides such as silica, and the like. Such supports will preferably take the form of small beads, pellets, disks, films, or other conventional forms, although other forms may be used.
A preferred solid support is an organic or inorganic polymer, to which the phosphorus can be covalently attached through a side chain or pendant group of the polymeric backbone. The polymer may be crosslinked or modified. Suitable preferred polymers useful in the preparation of a supported phosphine compound or a combinatorial library of supported phosphine compounds, include polyolefins, polyacrylates, polymethacrylates, and copolymers thereof that meet the general criteria described above. A more preferred polymeric support is polystyrene wherein the phosphorus is attached to a pendant phenyl group on the polystyrene backbone. Most preferred is polystyrene, crosslinked with divinylbenzene. Specifically, polystyrenes commonly used for solid phase synthesis have been used. These particular resins are crosslinked with from 1 to 10 wt % divinylbenzene. The styrene moieties are substituted in the para or meta positions. Only a portion of the styrene moieties are substituted, typically resulting in functional group loadings of approximately 0.2 to 2.0 mmole per gram of resin, although this value may be higher or lower.
Preferred embodiments for the novel supported phosphine compositions and for combinatorial libraries of supported phosphine compounds are selected from the group of Formulae 1A-7A: 
where Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.
Preferred compounds include those where L is xe2x80x94CH2xe2x80x94. Also preferred are those where A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl and t-butyl; R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3 and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Most preferred compounds are those where the solid support is polystyrene (crosslinked with divinylbenzene) and where Lxe2x95x90CH2 and Z, A, R1, R2, and R3 are as shown in Tables 1-5 below.
Another aspect of this invention is a combinatorial library of supported phosphine compounds selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7 wherein SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds;
A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and
R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring.
As used herein, a combinatorial library is an intentionally created collection of a plurality of differing molecules which can be prepared by selected synthetic means and screened for a desired activity or characteristic in a variety of formats (e.g., libraries of soluble molecules, libraries of compounds attached to resin beads, silica chips, or other solid supports). The libraries are generally prepared such that the compounds are in approximately equimolar quantities, and are prepared by combinatorial synthesis. Combinatorial synthesis refers to the parallel synthesis of diverse compounds by sequential additions of multiple choices of reagents which leads to the generation of large chemical libraries containing related molecules having molecular diversity. Screening methods for libraries vary greatly and are dependent upon a desired activity, the size of library, and the class of compounds in the library.
The libraries of the instant invention can be of any type. These types include but are not limited to arrays and mixtures. Arrays are libraries in which the individual compounds are simultaneously synthesized in spatially segregated locations, typically identified by their location on a grid. Mixture libraries contain a mixture of compounds that are simultaneously synthesized and assayed. Identification of the most active compound is then performed by any of several techniques well known in the combinatorial art, such as deconvolution.
A preferred solid support for the combinatorial libraries of the instant invention is an organic or inorganic polymer as described above, to which the phosphorus can be covalently attached through a side chain or pendant group of the polymeric backbone.
Preferred embodiments for the novel combinatorial libraries of phosphine compositions are shown in Formulae 1A-7A where Z is a divalent attaching group covalently attached to at least one phosphorus in each phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.
Preferred compounds include those where L is xe2x80x94CH2xe2x80x94. Also preferred are those where A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl and t-butyl; R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Most preferred libraries are those where the solid support is polystyrene (crosslinked with divinylbenzene) and where L, Z, A, R1, R2, and R3 are as shown in Tables 6-7 below.
Any reaction in which the phosphorus is covalently attached to the solid support may be used to prepare the compounds and libraries represented by Formula 1-7, such as those described in Encyclopedia of Inorganic Chemistry, John Wiley and Sons, Vol. 6, pg. 3149-3213, herein incorporated by reference.
One such scheme, another aspect of this invention, comprises the steps of contacting (i) a phosphine selected from the group consisting of XPR1R2, XR3Pxe2x80x94Axe2x80x94PR1R2, HP(xe2x95x90O)R1R2, HP(xe2x95x90O)R3xe2x80x94Axe2x80x94PR1R2, and HP(xe2x95x90O)R3xe2x80x94Axe2x80x94P(xe2x95x90O)R1R2 wherein X is a halogen, with (ii) a solid support, resulting in at least one P in the phosphine attached indirectly or directly to the solid support via one or more covalent bonds, and optionally replacing one or more of R1, R2 or R3 with any other R1, R2 or R3 defined above. To create a library, one or more phosphines are reacted with one or more solid supports, generating a plurality of supported phosphine compounds.
One embodiment of attaching the P to the solid support is via the reaction of the halogen or hydrogen bonded to the phosphorus in the phosphine with a nucleophilic group that is covalently attached to a solid support. The term nucleophilic group is a term well recognized in the art and refers to chemical moieties having a reactive pair of electrons. This scheme can easily be adapted for combinatorial synthesis.
When using diphosphines to prepare the compounds of the instant invention, the ratio of the reagents determines whether the product has one P in each phosphine or both P in each phosphine attached covalently to the solid support. When at least 2 molar equivalents of a phosphine of the Formula XR3Pxe2x80x94Axe2x80x94PR1R2 is contacted with no more than one molar equivalent of the nucleophilic group attached to the solid support, the resulting product will have one P in the phosphine covalently bonded to the solid support. When no more than one molar equivalent of a phosphine of the Formula XR3Pxe2x80x94Axe2x80x94PR1R2 is contacted with at least 2 molar equivalents of the nucleophilic group attached to the solid support, the resulting product will have both P in the phosphine covalently bonded to the solid support.
Other preferred processes of the instant invention to prepare a supported phosphine compound or a library of supported phosphine compounds include where: (1) the supported phosphine compound is of Formula 1A and the process comprises the steps of contacting at least 2 molar equivalents of a phosphine of the Formula XR3Pxe2x80x94Axe2x80x94PR1R2 with no more than one molar equivalent of Z, resulting in one P in the phosphine being covalently bonded to the Z; (2) the supported phosphine compound is of Formula 2A and the process comprises the steps of contacting a phosphine of the Formula PR1R2X with the solid support, resulting in one P in the phosphine being covalently bonded to Z; (3) the supported phosphine compound is of Formula 3A and the process comprises the steps of contacting no more than one molar equivalent of a phosphine of the Formula XR3Pxe2x80x94Axe2x80x94PR1R2 with at least two molar equivalents of Z, resulting in both of the P in the phosphine being covalently bonded to the Z; (4) the supported phosphine compound is of Formula 4A and the process comprises the steps of contacting a phosphine of the Formula HP(xe2x95x90O)R3xe2x80x94Axe2x80x94PR1R2 with the solid support, resulting in one P in the phosphine being covalently bonded to Z, and (5) where the supported phosphine compound is of Formula 5A and the process comprises the steps of contacting a phosphine of the Formula HP(xe2x95x90O)R1R2 with a solid support of the formula 
wherein the P in the solid support is covalently bonded to Z and Zxe2x80x2 is selected from the group consisting of alkenyls, resulting in the P in the phosphine being covalently bonded to the P in the solid support via Zxe2x80x2.
More preferred is where SS is polystyrene, L is xe2x80x94CH2xe2x80x94, Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94 and xe2x80x94Oxe2x80x94, A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms, R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl, and R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.
Examples of reactions to prepare the compounds are shown but not limited to those in Scheme 1 below, where X is a halogen, M is any metal, R can be one or more of R1, R2, or R3, and R1, R2, R3, R4, Z, and A are as defined above. The Z, O, S, and N substituents are covalently attached to the solid support. 
Any of the substituents in the above compounds may be replaced by other functional groups using any procedure known in the art. One or all of the substituents can be reacted in a single reaction, depending on the choice of reactants and reaction conditions. These reactions can easily be adapted for combinatorial processes. Examples of suitable procedures are shown by but not limited to those depicted in Scheme 2 below, where X, M, and A are as defined above, and R indicates any of R1, R2, or R3, as defined above. Examples of suitable definitions for M include Mg, Li, and Zn. Y is any linking group with the proper orientation or with enough flexibility to allow the reaction to proceed. The choice of Y will determine whether the ring is formed between two phosphorus atoms or on one phosphorus atom. Examples of suitable linking groups include hydrocarbylene, substituted hydrocarbylene, and organometallic compounds. 
The processes of the instant invention and of Schemes 1-2 are preferably performed under dry, inert atmosphere with dry, deoxygenated solvents. Any solvent is suitable provided that it is inert to all reagents and products. Optimum temperatures are about xe2x88x9280 to about 200xc2x0 C., preferably about xe2x88x9280 to about 150xc2x0 C.
The invention provides for novel phosphine compositions of Formulae 8-12: 
where A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.
Preferred embodiments for these phosphine compositions are where A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other R5, R6, R7, and R8 form a ring. More preferred embodiments for Formula 8 are where at least one of R5, R6, R7, and R8 are different from the rest. Most preferred embodiments are shown in Tables 8-12 below.
The invention also provides for combinatorial libraries of the phosphine compositions of Formulae 8-12 where A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4 and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring. The libraries can be including arrays and any type of mixtures.
Preferred embodiments for these libraries are where A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring. More preferred embodiments for Formula 8 are where at least one of R5, R6, R7, and R8 are different from the rest. Most preferred embodiments are shown in Tables 13-14 below.
Another aspect of this invention is a process to prepare the phosphine compound of Formulae 8-12 or a combinatorial library of phosphine compounds of Formulae 8-12 where A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring. The process comprises the steps of:
(a) contacting (i) a supported phosphine selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7 where SS is a solid support wherein at least one P in the phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring; with (ii) a compound of the Formula ER9, wherein E is an electrophilic group and R9 is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; thereby forming the corresponding compound of Formulae 1, 2, 3, 4, 5, 6, and 7; and
(b) optionally replacing one or more of R5, R6, R7, and R8 with any R5, R6, R7, and R8.
To create a library, one or more supported phosphines are reacted with one or more compounds of the Formula ER9, generating a plurality of phosphine compounds.
A preferred process is where the phosphine or the library of phosphines produced by the above process is substituted asymmetrically; such compounds are difficult to prepare by techniques previously known in the art. The solid support serves essentially as a protecting group, facilitating the attachment of at least one substituent on a phosphorus that is different than the others. The process operates without any complicated separation or purification steps needed.
When the bisphosphine compounds of the present invention are unsymmetrically substituted, whether they are supported or unsupported, two isomers are present, cis and trans, as illustrated below. 
The processes described herein prepare a 50/50 mixture of these two isomers. The isomers can be isolated by standard techniques such as recrystallization.
In the above process, E is any electrophilic group that will cleave the covalent bond attaching the phosphorus to the solid support. The term electrophilic group is a term well recognized in the art and refers to chemical moieties, which can accept a pair of electrons from a nucleophilic group as defined above. Suitable electrophilic groups include xe2x80x94OH, trimethylsilyl, PCl2, halogens, and protons donated from compounds such as acids, alcohols, or amines.
In the instance where ER5 is water, the resulting POH group would rearrange to yield to form the compounds of Formula 10, 11, or 12. These compounds can also be formed from any other of Formulae 8-12 via the replacement of one or more of R5, R6, R7, and R8 with an xe2x80x94OH group using any method known in the art. An equivalent rearrangement occurs when a PSH group is present.
Preferred processes for the preparation of the phosphine compounds or the library of phosphine compounds of the instant invention include those wherein the supported phosphine is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A where Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms; A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.
Also preferred is where E is selected from the group consisting of hydrogen, PCl2, and SiMe3, and where R5 is a halogen.
After cleavage from the solid support, R5, R6, R7, and R8 may be replaced with any other substituent using any method known in the art, in order to prepare a further range of compounds.
The process is preferably performed under dry, inert atmosphere with dry, deoxygenated solvents. Any solvent is suitable provided that it is inert to all reagents and products. Optimum temperatures are about xe2x88x9280 to about 200xc2x0 C., preferably about xe2x88x9280 to about 150xc2x0 C.
Preferred versions of the process to prepare the phosphine compounds or the library of phosphine compounds of the instant invention include those where the supported phosphine compound is selected from the group consisting of Formulae 1 and 3 and the corresponding phosphine compound is of Formula 8, the supported phosphine compound is of Formula 2 and the corresponding phosphine compound is of Formula 9; the supported phosphine compound is of Formula 4 and the phosphine compound is of Formula 10, the supported phosphine compound is selected from the group consisting of Formulae 3 and 5 and the phosphine compound is of Formula 11, and the supported phosphine compound is of Formula 2, and the phosphine compound is of Formula 12. More preferred is where Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94, A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms, R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.
The phosphorus compounds and libraries described herein, both supported and unsupported, can be utilized as ligands for catalytic compounds.
Another aspect of the instant invention is a coordination compound comprising one or more transition metals complexed to a ligand selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7 where SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds, A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups, R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring.
xe2x80x9cCoordination compoundxe2x80x9d refers to a compound formed by the union of a metal ion (usually a transition metal) with a non-metallic ion or molecule called a ligand or complexing agent.
The transition metals are hereby defined as metals of atomic weight 21 through 83. Preferably, the transition metal is from Periodic Group VIII, hereby defined as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt. Preferred is Rh. The complex can be made by any synthetic method known in the art, either through direct reaction or via the use of a transition metal precursor. Many of these techniques are described in Hartley, ibid.
A preferred embodiment for the coordination compound is where SS is selected from the group consisting of polyolefins, polyacrylates, polymethacrylates, and copolymers thereof, and wherein the transition metals are selected from Periodic Group VIII.
Another preferred embodiment of the coordination compound is where the ligand is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A where Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94 where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen, and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.
More preferred is where the ligand is Formula 1A where SS is polystyrene, L is xe2x80x94CH2xe2x80x94, A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms, Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94, R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl and t-butyl, R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl or alkyl ring, and the transition metal is Rh. Most preferred is where the ligand is polymer-bound 1-(1,1-di-n-propylphosphino)-2-n-propyl phospinioethane.
Most preferred is where the ligand is Formula 1A, L is (CH2), Z is N(t-butyl), A is (CH2)2, R is n-propyl, R2 is n-propyl, R3 is n-propyl, and M is Rh.
Another aspect of the invention is a combinatorial library of coordination compounds comprising one or more transition metals complexed to one or more ligands selected from the group consisting of Formulae 1, 2, 3, 4, 5, 6, and 7 where SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds, A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups, R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring.
A preferred embodiment is where SS is selected from the group consisting of polyolefins, polyacrylates, polymethacrylates, and copolymers thereof, and wherein the transition metals are selected from Periodic Group VIII.
Also preferred is where the ligand is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A where Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, and xe2x80x94NR4xe2x80x94, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen, and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.
More preferred is where the ligand is Formula 1A, SS is polystyrene, L is xe2x80x94CH2xe2x80x94, A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms, Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94, R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl, R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring, and the transition metal is Rh.
Another aspect of the instant invention are novel combinatorial libraries of coordination compounds comprising one or more transition metals complexed to one or more ligands selected from the group consisting of Formulae 8, 9, 10, 11, and 12 where A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups, R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.
Preferred is the combinatorial library where A is an optionally-substituted carbon chain of 1-3 carbon atoms, R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring, and the transition metals are selected from Periodic Group VIII.
Also preferred is where the ligands are of Formula 8, and where at least one of R5, R6, R7, and R8 are different from the rest.
More preferred is where A is an optionally-substituted carbon chain of 1-3 carbon atoms, R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring, and the transition metal is Pd.
Most preferred is where the ligand is of Formula 8, A=(CH2)2, and where R5, R6, R7, R8, and M are shown below:
The phosphine coordination compounds and libraries of phosphine coordination compounds can be prepared by any method known in the art, but preferably by those described herein.
Another aspect of the instant invention is a novel reaction to prepare coumarin, useful as an intermediate in pharmaceutical preparations, by contacting salicylaldehyde with an acrylate of the formula 
wherein R10 is an alkyl group of 1-6 carbons. Preferred is where R10 is n-butyl. Salicylaldehyde is converted via decarbonylation and insertion of an acrylate, followed by ring closure, as shown in Scheme 3. 
A preferred process is where the reaction is performed in the presence of a catalytic amount of the novel, phosphine coordination compounds of the instant invention, described above. Preferred is where the coordination compounds comprise a ligand selected from the group consisting of Formulae 1-7. Most preferred is where the metal is Rh, and the ligand is of Formula 1A where wherein SS is polystyrene, L is xe2x80x94CH2xe2x80x94, A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms, Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, xe2x80x94(NR4)xe2x80x94, and xe2x80x94Oxe2x80x94, R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl, R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring. Most preferred is where SS is polystyrene, A is (CH2)2, Z is N(t-butyl), and R1, R2, and R3 are n-propyl.
Any solvent is suitable for this process provided that it is inert to all reagents and products. Optimum temperatures are about xe2x88x9280 to about 200xc2x0 C., preferably about xe2x88x9280 to about 150xc2x0 C.